CN113736464B - Rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material, battery and preparation method - Google Patents
Rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material, battery and preparation method Download PDFInfo
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Abstract
The invention discloses a rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material, a battery and a preparation method thereof, belonging to the technical field of perovskite solar cells, wherein the rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material is prepared by doping Li element and compounding g-C 3 N 4 The rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material with new components is obtained, and the modification mode can improve the light conversion performance and the electric conduction performance of UCNPs. The invention also provides the preparation of Li + :UCNPs/g‑C 3 N 4 A method of preparing a composite material and a method of preparing a perovskite solar cell using the same. The Li is + :UCNPs/g‑C 3 N 4 The composite material can change the frequency of incident sunlight, convert near infrared light into visible light which can be absorbed by the battery, thereby generating extra photocurrent and improving the photoelectric conversion efficiency of the perovskite solar battery.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a rare earth up-conversion nanoparticle/graphite-like phase carbon nitride composite material, a battery and a preparation method.
Background
All-solid organic-inorganic metal lead halide perovskite solar cell (APbX) 3 : wherein a=cs, CH 3 NH 3 Or CH(NH 2 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the X=cl, br or I) as a new generation solar cell, is highly colored in the photovoltaic field. Currently, continued improvement in perovskite solar cell efficiency presents a significant challenge. By CH 3 NH 3 PbI 3 The perovskite layer can only absorb light with the wavelength of 280-800 nm and only occupies a small part of the solar spectrum (280-2500 nm). Therefore, the improvement of the response range of the battery to the solar spectrum and the reduction of the loss of incident photons are key to further improving the photoelectric conversion efficiency of the battery.
The publication No. CN108816266A discloses a YF/g-C 3 N 4 Composite material and application thereof in photocatalysis, and Y (NO 3 ) 3 、Yb(NO 3 ) 3 、Tm(NO 3 ) 3 And Er (NO) 3 ) 3 Mixing, taking water as a solvent, adding NaF to form a suspension colloid, and performing hydrothermal reaction to obtain an up-conversion material YF; then g-C 3 N 4 Dissolved in HNO 3 After the colloidal suspension mixture is obtained, the pH value is adjusted to be neutral; finally, adding up-conversion material YF into the mixed solution, stirring uniformly, calcining to obtain YF/g-C 3 N 4 A composite material. The doping treatment of the up-conversion material is carried out on the carbon nitride, so that the defects of narrow forbidden band width of the carbon nitride and insufficient sunlight utilization rate are effectively overcome, the prepared composite material has higher sunlight absorption utilization rate, and the material is suitable for being used as a photocatalyst.
How to develop a novel material, which is suitable for perovskite solar cells, and improving the photoelectric conversion efficiency of the cells is a technical problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material, a battery and a preparation method thereof, wherein Li is as follows + :UCNPs/g-C 3 N 4 Perovskite solar cell prepared by using composite material as up-conversion material, li + :UCNPs/g-C 3 N 4 The composite material can convert near infrared light into visible light, and expand perovskiteThe solar cell absorbs near infrared light, improves the photoelectric conversion efficiency of the cell, and has stable performance and good manufacturability.
To achieve the above object, according to a first aspect of the present invention, there is provided a rare earth up-conversion nanoparticle/graphite-like phase carbon nitride composite material which is Li + Doped NaYbF 4 :Ho 3+ Rare earth up-conversion nanoparticles and g-C 3 N 4 Obtained by post-reaction compounding.
According to a second aspect of the present invention, there is provided a method for preparing a rare earth up-conversion nanoparticle/graphite-like phase carbon nitride composite material, comprising the steps of:
(1) Nitrate Yb (NO) of lanthanoid 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 O is added into an organic volatile solvent and stirred uniformly to prepare a first solution,
(2) Dissolving sodium fluoride and lithium nitrate in the same organic volatile solvent as in the step (1), uniformly stirring to prepare a second solution,
(3) Slowly adding the second solution into the first solution, adding acid to adjust the pH value to 4-6, preparing a third solution,
(4) Transferring the third solution into a high-pressure reaction kettle, heating in a hydrothermal box for 4-24 h at 180-220 ℃, then naturally cooling,
(5) Centrifuging and washing the third solution after the hydrothermal treatment until the pH value is 6-7, and annealing the obtained precipitate for 2-3 hours at 500-550 ℃ to obtain Li + The particle size of the doped rare earth up-conversion particle material is 50 nm-100 nm,
(6) Li is mixed with + The doped rare earth up-conversion nano-particle material is dispersed in the same organic volatile solvent as in the step (1) to obtain a fourth solution,
will g-C 3 N 4 Adding into deionized water, stirring to obtain g-C 3 N 4 The mixed liquid is prepared into a mixed liquid,
(7) Will g-C 3 N 4 Adding the mixed solution into the fourth solution to obtain suspension, and suspendingAdding the floating liquid into a high-pressure reaction kettle, maintaining the temperature at 180-200 ℃ for 20-24 h, centrifugally collecting the product, and vacuum drying at 80-90 ℃ for 12-16 h to obtain Li + Doped rare earth up-conversion nano-particles/graphite-like phase carbon nitride composite materials.
Further, the molar ratio of Yb to Ho in the first solution in the step (1) is (40-60): 1.
Further, in the step (1), the organic volatile solvent is ethylene glycol.
Further, in the step (6), g-C 3 N 4 The preparation method of (2) is as follows:
(1) Placing urea into a crucible, heating to 550-600 ℃ at a speed of 2-3 ℃/min, calcining for 2-3 h in a muffle furnace, naturally cooling to room temperature to obtain yellow solid,
(2) Heating the yellow solid in the step (1) to 500-600 ℃ again at the speed of 2-3 ℃/min, calcining in a muffle furnace for 2-3 h, naturally cooling to room temperature, and obtaining light yellow solid which is graphite-like phase carbon nitride g-C 3 N 4 。
Further, in the suspension of step (7), li + Mass and g-C of doped rare earth up-conversion nanoparticles 3 N 4 The mass ratio is as follows: 2-3 g Li + The doped rare earth up-conversion nano particles are correspondingly matched with 100-400 mg g-C 3 N 4 。
Further, the acid added in the step (3) is HNO with the concentration of 65 percent 3 。
According to a third aspect of the present invention there is also provided a solar cell employing a rare earth up-conversion nanoparticle/graphite-like phase carbon nitride composite material as described above for the preparation of a perovskite absorber layer.
According to a fourth aspect of the present invention, there is also provided a method of preparing a solar cell as described above, comprising the steps of:
(1) Cleaning the FTO conductive glass substrate to obtain a clean and dry FTO conductive glass substrate,
(2) Dissolving stannous chloride dihydrate and urea in deionized water, oxidizing into tin oxide solution in air to obtain precursor solution of an electron transport layer, spin-coating the precursor solution of the electron transport layer on the FTO conductive glass substrate obtained in the step (1), annealing for 10-30 min at 150-180 ℃ to obtain the electron transport layer,
(3) Li is mixed with + Spin-coating the precursor solution of the doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material on the electron transmission layer in the step (2), annealing for 10-30 min at 70-90 ℃ to obtain an up-conversion nano-composite material layer,
the Li is + The precursor solution of the doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material is obtained by dispersing the nano-composite material in ethanol solvent,
(4) Will CH 3 NH 3 PbI 3 The mixed solvent of the solution, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is prepared according to the volume ratio of 9:1 preparing a perovskite precursor solution, spin-coating the perovskite precursor solution on an up-conversion nano composite material layer, dropwise adding chlorobenzene before spin-coating is finished, heating for 5-15 min at 90-110 ℃ to obtain a perovskite absorption layer,
(5) And preparing an electrode on the perovskite absorption layer by adopting a screen printing method.
Further, it comprises the following steps: in the step (3), annealing is carried out for 10 min-30 min at 80 ℃ to obtain an up-conversion nano composite material layer, and in the step (4), heating is carried out for 10min at 100 ℃ to obtain the perovskite absorption layer.
In general, the above technical solutions conceived by the present invention have the following beneficial effects compared with the prior art:
1. li prepared by the invention + The doped rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material has up-conversion luminescence property, can effectively absorb near infrared light, and converts the near infrared light in sunlight into visible light, and is characterized in that Li + And g-C 3 N 4 The up-conversion efficiency and the electric conduction performance of the nano material are further improved by adding the nano material. In the present invention, yb in the up-conversion luminescent material 3+ The particles are sensitizer, can effectively absorb external energy and transmit the external energy to the activator, the dielectric configuration of the sensitizer is 4f, the energy state structure is simple, and the sensitizer has only one excitation state, ho 3+ The particles are activators, are luminescent centers in the up-conversion material, ho 3+ The particles have rich energy levels, and Ho is caused by the electron shielding effect of the 4f energy level 3+ The particles have longer energy level life, are better activators and are made of Yb 3+ And Ho 3+ The double-doped up-conversion luminescent material is one of better double-doped systems, and uses Yb 3+ The maximum absorption cross section of (a) is in the near infrared region (980 nm), and can effectively transfer energy from Yb 3+ Transfer to activator Ho 3+ It is converted into visible light within the absorption range (200-800 nm) of the perovskite layer, so that the perovskite layer absorbs the visible light energy again to generate additional photocurrent.
2. The up-conversion nano material is compounded with the organic semiconductor polymer and then applied to the perovskite solar cell, so that the method has the following advantages: firstly, an up-conversion luminescent material layer of the up-conversion nanocomposite obtained by spin coating is used as an interface modification layer, so that the defect state of the surface of a perovskite layer can be reduced; and secondly, as an up-conversion nanocomposite, the perovskite solar cell can absorb near infrared light and convert the near infrared light into visible light which can be absorbed by the perovskite absorption layer, so that the exciton number is increased, and the photoelectric conversion efficiency of the perovskite solar cell is improved.
Drawings
FIG. 1 is a graphite-like phase carbon nitride, li + Rare earth doped up-conversion nanoparticles and Li + An X-ray diffraction pattern of the doped rare earth up-conversion nanoparticle/graphite-like phase carbon nitride composite material;
FIG. 2 is a rare earth upconversion nanoparticle, li + Doped rare earth up-conversion nanoparticles and Li + Up-conversion luminescence diagram of doped rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material, excitation light source is 980nm laser;
FIG. 3 is a graphite-like phase carbon nitride, li + Rare earth doped up-conversion nanoparticles and Li + Doped rare earth up-conversion nanoparticles/graphite-likeAn ultraviolet-visible-infrared absorption spectrum of the phase carbon nitride composite material;
FIG. 4 is a schematic diagram of the use of non-spin-coated Li + Perovskite solar cell of doped rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material and spin-coated Li + Current-voltage (I-V) profile of a perovskite solar cell with doped rare earth up-conversion nanoparticle/graphite-like phase carbon nitride composite as up-conversion luminescent material layer.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention relates to a Li + Doped rare earth UCNPs/g-C 3 N 4 Composite material, method of preparation and perovskite solar cell and method of preparation of cell made from said composite material. In the present invention, li is prepared by + Rare earth doped up-conversion nanoparticle materials (UCNPs) are used for changing the frequency of incident sunlight, and converting near infrared light into visible light which can be absorbed by a battery, so that extra photocurrent is generated, and the battery efficiency can be improved. UCNPs have poor conductivity, prevent electron transmission, and improve conductivity and energy utilization rate by doping a composite polymer semiconductor. Graphite-like phase carbon nitride (g-C) 3 N 4 ) The perovskite nano-material has an easily-adjustable energy band structure and a highly transparent morphology, and the superior electron mobility and higher conductivity can make up the defect of poor conductivity of the up-conversion nano-particle material, and the functional groups on the perovskite nano-material can further passivate perovskite defects. UCNPs and g-C 3 N 4 The combination of the perovskite photoelectric conversion device can better improve conductivity and more effectively transfer energy, so that the perovskite photoelectric conversion efficiency is more effectively improved.
In the laboratory development stage, li + The preparation method of the doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material can comprise the following steps:
(one) Synthesis of Li + Preparation of doped rare earth up-conversion nanoparticles:
(1) Nitrate of lanthanoid element (6-7 mmol Yb (NO) 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 O) adding the mixture into 2-7 mL of glycol, and stirring to prepare a solution A for standby. The mol ratio of Yb to Ho is (40-60): 1;
(2) Dissolving 0.01-0.02 mol of sodium fluoride and 0.01-0.02 mol of lithium nitrate in 20-70 mL of ethylene glycol, and stirring to prepare solution B;
(3) Slowly adding the solution B into the process of (1) while stirring to prepare a solution A, and using HNO 3 (65%) adjusting the pH value to 4-6 to prepare solution C;
(4) Transferring the solution C into a polytetrafluoroethylene autoclave, heating the solution C in a hydrothermal box for 4-24 hours at the temperature of 180-220 ℃, and naturally cooling the solution C;
(5) Centrifuging and washing the solution C after hydrothermal treatment until the pH value is close to 6-7, and annealing the obtained precipitate for 2-3 h at 500-550 ℃ to obtain Li + The doped rare earth upconverts the nanoparticle material.
(II) preparation of synthetic graphite-like phase carbon nitride:
(1) Placing 5-10 g urea into a ceramic crucible, heating to 550-600 ℃ at a speed of 2-3 ℃/min, and calcining in a muffle furnace for 2-3 h. Naturally cooling to room temperature to obtain yellow solid D;
(2) The yellow solid D is heated to 500-600 ℃ again at the speed of 2-3 ℃/min, and is calcined in a muffle furnace for 2-3 h. Naturally cooling to room temperature to obtain pale yellow solid E which is graphite-like carbon nitride.
(III) Synthesis of Li + Preparation of doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material:
(1) 0.2 to 0.3g of Li + Dispersing the doped rare earth up-conversion nano particles into 10-15 mL of ethanol through ultrasonic treatment to obtain a solution (1);
(2) Dispersing 10-40 mg g-C in 15-20 mL deionized water 3 N 4 Adding the mixture into the solution (1), and stirring uniformly at room temperature to obtain a suspension (2).
(3) Transferring the suspension (2) into a high-pressure reaction kettle, and keeping the temperature of 180-200 ℃ for 20-24 h. And centrifugally collecting the product and vacuum drying at 80-90 ℃ for 12-16 h. Finally obtain Li + Doped rare earth up-conversion nano-particles/graphite-like phase carbon nitride composite materials.
Li prepared by the method + The doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material can be applied as an up-conversion material. Above Li + The doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material can be used for preparing perovskite solar cells.
In the laboratory research and development stage, the preparation method of the perovskite solar cell comprises the following steps:
(1) Cleaning an FTO conductive glass substrate: sequentially placing FTO conductive glass into detergent water, acetone, isopropanol and ethanol, ultrasonically cleaning for 20-30 min, and then irradiating for 15-25 min by UV;
(2) Preparing an electron transport layer: the precursor solution of the electron transport layer is tin oxide solution formed by oxidizing 0.3-0.4 g stannous chloride dihydrate, 0.08-0.09 g urea and 10-15 mL deionized water in air, the precursor solution is spin-coated (4000 rpm, 30 s) on the cleaned FTO conductive glass, and annealing treatment is carried out for 10-30 min at 150-180 ℃ to obtain the electron transport layer;
(3) Preparation of the up-conversion nanocomposite layer: li is mixed with + Spin-coating (4000 rpm, 30 s) the precursor solution of the doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material on the electron transmission layer, and annealing at 80 ℃ for 10-30 min to obtain the up-conversion nano-composite material layer. The precursor solution is prepared by dispersing a nano composite material in an ethanol solvent;
(4) Preparation of perovskite absorption layer: will be 1.3M CH 3 NH 3 PbI 3 The volume ratio of the solution is 9:1, preparing a mixed solvent of Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and obtaining a perovskite precursor solution; spin coating perovskite precursor solution on the up-conversion nano composite material layer, and spin coating the junction100 mu L of chlorobenzene is added dropwise 16s before the bundling; finally heating for 10min at 100 ℃ to obtain the perovskite absorption layer;
(5) Preparation of a carbon electrode: preparing a carbon electrode on the perovskite absorption layer by adopting a screen printing method;
(6) The perovskite solar cell is thus obtained.
In order to better illustrate the process of the present invention, it is further elaborated below in connection with specific examples.
Example 1: li (Li) + Preparation of doped rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material
Li (lithium ion battery) + The preparation method of the doped rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material comprises the following steps:
1. synthesis of Li + Preparation of doped rare earth up-conversion nanoparticles:
(1) Nitrate of lanthanide (6.6 mmol Yb (NO) 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 O) was added to 3mL of ethylene glycol and stirred for 8 hours to prepare solution A for use. The mol ratio of Yb to Ho is 47:1;
(2) Dissolving 0.017mol of sodium fluoride and 0.017mol of lithium nitrate in 20mL of ethylene glycol, and stirring for 12 hours to prepare a solution B;
(3) Slowly adding the solution B into the process of (1) while stirring to prepare a solution A, and using HNO 3 (65%) the pH was adjusted to 4 to prepare solution C;
(4) Transferring the solution C into a polytetrafluoroethylene autoclave, heating the solution C in a hydrothermal box at the temperature of 200 ℃ for 12 hours, and naturally cooling the solution C;
(5) Centrifuging and washing the hydrothermal solution C until the pH value is close to 7, and annealing the obtained precipitate at 500 ℃ for 2 hours to obtain Li + The doped rare earth upconverts the nanoparticle material.
2. Preparation of synthetic graphite-like phase carbon nitride:
(1) 10g of urea was placed in a ceramic crucible and heated to 550℃at a rate of 3℃per minute and calcined in a muffle furnace for 2 hours. Naturally cooling to room temperature to obtain yellow solid D;
(2) The yellow solid D was again warmed to 500 ℃ at a rate of 3 ℃/min and calcined in a muffle furnace for 2h. Naturally cooling to room temperature to obtain pale yellow solid E which is graphite-like carbon nitride.
3. Synthesis of Li + Preparation of doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material:
(1) Will 0.2g Li + Dispersing the doped rare earth up-conversion nano particles into 10mL of ethanol through ultrasonic treatment to obtain a solution (1);
(2) 30mg g-C of the dispersion in 20mL of deionized water 3 N 4 Adding the mixture into the solution (1), and uniformly stirring the mixture for 12 hours at room temperature to obtain a suspension (2);
(3) The suspension (2) was transferred to an autoclave, kept at 180℃for 24 hours, and the product was collected by centrifugation and dried in vacuo at 80℃for 12 hours. Finally obtain Li + Doped rare earth up-conversion nano-particles/graphite-like phase carbon nitride composite materials. The XRD pattern of the resulting nanomaterial is shown in figure 1.
FIG. 1 is a graphite-like phase carbon nitride, li + Rare earth doped up-conversion nanoparticles and Li + As can be seen from FIG. 1, two characteristic peaks at 12.8 degrees and 27.9 degrees can illustrate that g-C is successfully synthesized 3 N 4 A material. The nano material obtained by experiment is NaYbF of cubic alpha phase 4 :Ho 3+ Characteristic peaks at 28.5, 33.1, 47.4, 56.3 and 59.0 degrees are assigned to the (111), (200), (220), (311) and (222) crystal planes. The up-conversion nanomaterial part in the obtained up-conversion nanocomposite is converted into a hexagonal beta phase state, and a characteristic peak at 17.3 degrees of a (100) crystal plane appears. In addition, g-C is also present in the upconverting nanocomposite 3 N 4 Showing the hydrothermal loading of the two materials together.
Comparative test 1
To illustrate the up-conversion luminescence properties of the nanomaterial obtained in example 1, a comparative experiment one provided two control groups, the control group one being rare earth up-conversion nanoparticlesUCNPs preparation method is free from adding LiNO 3 、g-C 3 N 4 Except for this, the procedure is as in example 1; control group II is Li + Doped rare earth up-conversion nanoparticles, li + The UCNPs preparation method is not added with g-C 3 N 4 Except for this, the procedure of example 1 was repeated.
The two control groups of example 1 and comparative experiment one were subjected to an up-conversion luminescence test under 980nm laser excitation, and the up-conversion luminescence spectra are shown in fig. 2. FIG. 2 is a rare earth upconversion nanoparticle, li + Doped rare earth up-conversion nanoparticles and Li + The up-conversion luminescence graph of the doped rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material can be seen that the up-conversion nano composite material can be used as an up-conversion luminescence material layer, can convert near infrared light into visible light which can be absorbed by a perovskite solar cell, and can be used for preparing a light-emitting device by Li + Is (1) and g-C 3 N 4 Is a complex of Li + :UCNPs/g-C 3 N 4 The up-conversion luminous intensity of (c) is significantly enhanced.
Comparative test two
To illustrate the upconversion luminescence properties of the nanomaterial obtained in example 1, two control groups, g-C, were provided for comparative experiment two, the first control group being graphite-like phase carbon nitride 3 N 4 The preparation method of (2) is the same as that of example 1; control group II is Li + Doped rare earth up-conversion nanoparticles, li + The UCNPs preparation method is not added with g-C 3 N 4 Except for this, the procedure of example 1 was repeated. The ultraviolet-visible-infrared absorption test was performed under the same test conditions for example 1 and comparative test II, the results of the spectra are shown in FIG. 3, FIG. 3 is graphite-like phase carbon nitride, li + Rare earth doped up-conversion nanoparticles and Li + Ultraviolet-visible-infrared absorption spectrum diagram of doped rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material. From the figure, g-C 3 N 4 Has obvious absorption at 200-450 nm, and the absorption is weak. Li (Li) + UCNPs have obvious absorption peaks at 200-250 nm and 900-1000 nm, and the absorption of other wave bands is weak. Li (Li) + :UCNPs/g-C 3 N 4 The two materials are integrated, and the two materials have obvious absorption peaks at 200-250 nm and 900-1000 nm, and the absorption in the range of 250-350 nm is compared with Li + Enhancement of UCNPs.
Example 2: preparation of perovskite solar cell
A method for preparing a perovskite solar cell, comprising the steps of:
(1) Cleaning an FTO conductive glass substrate: sequentially placing FTO conductive glass into detergent water, acetone, isopropanol and ethanol, performing ultrasonic cleaning for 30min, and performing UV irradiation for 20min to obtain a clean FTO substrate;
(2) Preparing an electron transport layer: the precursor solution of the electron transport layer is tin oxide solution prepared by stirring and oxidizing 0.34g of stannous chloride dihydrate, 0.09g of urea and 10mL of deionized water in air, the precursor solution is spin-coated on the cleaned FTO conductive glass, the spin-coating rotating speed is 4000 r/min, annealing treatment is carried out for 10min at 180 ℃ to obtain the electron transport layer, and the obtained substrate is named as FTO/SnO 2 ；
(3) Preparation of the up-conversion nanocomposite layer: li is mixed with + The precursor solution of the doped rare earth up-conversion nano-particle/graphite-like carbon nitride composite material is screwed on the electron transmission layer, the rotation speed during the spin coating is 4000 rpm, and the annealing treatment is carried out for 10min at 80 ℃ to obtain an up-conversion nano-composite material layer, and the obtained substrate is named as FTO/SnO 2 /Li + :UCNPs/g-C 3 N 4 The precursor solution is obtained by dispersing a nano composite material in an ethanol solvent;
the Li is + :UCNPs/g-C 3 N 4 The preparation method of the precursor solution of the material is the same as that of the suspension in example 1;
(4) Preparation of perovskite absorption layer: will be 1.3M CH 3 NH 3 PbI 3 The volume ratio of the solution is 9:1, preparing a mixed solvent of Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and obtaining a perovskite precursor solution; spin-coating perovskite precursor solution on the up-conversion nano composite material layer, wherein the rotating speed during spin-coating is 1000 revolutions per minute,10s and 4000 rpm, 30s, and 16s before spin-coating was completed, 100 μl of chlorobenzene was added dropwise; finally heating for 10min at 100deg.C to obtain perovskite absorption layer, and the obtained substrate is FTO/SnO 2 /Li + :UCNPs/g-C 3 N 4 /Perovskite；
(5) Preparation of a carbon electrode: preparing a carbon electrode on the perovskite absorption layer by adopting a screen printing method, namely completing the preparation of the battery, wherein the obtained battery is named as FTO/SnO 2 /Li + :UCNPs/g-C 3 N 4 /Perovskite/Carbon。
Comparative test three
To illustrate the photovoltaic properties of the perovskite solar cell obtained in example 2, the control group of comparative experiment three was prepared in the same manner as in example 2 except that the upconverting nanocomposite layer was prepared, and the resulting control cell was designated as FTO/SnO 2 Perovskite/Carbon; the photoelectric performance test is carried out under the irradiation of an AM 1.5 solar simulator, and the data processing is carried out. The results are shown in Table 1 and FIG. 4, and the modified Li obtained in example 2 is compared with the unmodified perovskite solar cell + :UCNPs/g-C 3 N 4 The photovoltaic performance parameter of the cell of (2) includes the open circuit voltage (V oc ) Short-circuit current (J) sc ) The Filling Factor (FF) and the conversion efficiency (PCE) are all improved, li is obtained in example 2 + :UCNPs/g-C 3 N 4 The open circuit voltage of the modified battery is increased from 1.063V to 1.067V, and the short circuit current is increased from undoped 19.99mA/cm 2 Obviously increase to 22.55mA/cm 2 The packing factor is increased from 0.52 to 0.61 and the conversion efficiency (PCE) is increased from 11.01% to 14.78%.
TABLE 1 unmodified and Li + Doped rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material modified perovskite solar cell photoelectric performance parameter
Example 3: preparation of rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material
A preparation method of a rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material comprises the following steps:
(1) Nitrate Yb (NO) of lanthanoid 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 O is added into ethanol, and is stirred uniformly to prepare a first solution, the mol ratio of Yb to Ho in the first solution in the step (1) is 40:1,
(2) Dissolving sodium fluoride and lithium nitrate in the same organic volatile solvent as in the step (1), uniformly stirring to prepare a second solution,
(3) Slowly adding the second solution into the first solution, adding acid to adjust the pH value to 6, preparing a third solution,
(4) Transferring the third solution into a high-pressure reaction kettle, heating in a hydrothermal box at 180 ℃ for 24 hours, then naturally cooling,
(5) Centrifuging and washing the third solution after hydrothermal treatment until the pH value is 7, and annealing the obtained precipitate at 550 ℃ for 2 hours to obtain Li + The particle size of the doped rare earth up-conversion particle material is 50 nm-60 nm,
(6) Li is mixed with + Dispersing the doped rare earth up-conversion nano-particle material in the same organic volatile solvent as in the step (1) to obtain a fourth solution, and carrying out g-C 3 N 4 Adding into deionized water, stirring to obtain g-C 3 N 4 The mixed liquid is prepared into a mixed liquid,
wherein g-C 3 N 4 The preparation method of (2) is as follows:
firstly, urea is placed in a crucible, the temperature is raised to 600 ℃ at the speed of 3 ℃/min, the urea is calcined in a muffle furnace for 3 hours, and the urea is naturally cooled to room temperature to obtain yellow solid,
then, the yellow solid is heated to 500 ℃ again at the speed of 2 ℃/min, calcined in a muffle furnace for 2 hours, naturally cooled to room temperature, and the obtained pale yellow solid is similarGraphite phase carbon nitride g-C 3 N 4 。
(7) Will g-C 3 N 4 Adding the mixed solution into the fourth solution to obtain a suspension, wherein Li + Mass and g-C of doped rare earth up-conversion nanoparticles 3 N 4 The mass ratio is as follows: 2g Li + The doped rare earth up-conversion nano particles are correspondingly matched with 100mg g-C 3 N 4 . Adding the suspension into a high-pressure reaction kettle, maintaining at 180 ℃ for 24 hours, centrifugally collecting the product, and drying at 90 ℃ in vacuum for 16 hours to obtain Li + Doped rare earth up-conversion nano-particles/graphite-like phase carbon nitride composite materials.
Example 4: preparation of rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material
A preparation method of a rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material comprises the following steps:
(1) Nitrate Yb (NO) of lanthanoid 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 O is added into ethanol, and is stirred uniformly to prepare a first solution, the mol ratio of Yb to Ho in the first solution in the step (1) is 60:1,
(2) Dissolving sodium fluoride and lithium nitrate in the same organic volatile solvent as in the step (1), uniformly stirring to prepare a second solution,
(3) Slowly adding the second solution into the first solution, adding acid to adjust the pH value to 4, preparing a third solution,
(4) Transferring the third solution into a high-pressure reaction kettle, heating in a hydrothermal box for 4h at 220 ℃, then naturally cooling,
(5) Centrifuging and washing the third solution after hydrothermal treatment until the pH value is 6, and annealing the obtained precipitate at 500 ℃ for 3 hours to obtain Li + The particle size of the doped rare earth up-conversion particle material is 90 nm-100 nm,
(6) Li is mixed with + Dispersing the doped rare earth up-conversion nano-particle material in the same organic volatile solvent as in the step (1) to obtain a fourth solution, and carrying out g-C 3 N 4 Add to removeIn ion water, stirring uniformly to obtain g-C 3 N 4 The mixed liquid is prepared into a mixed liquid,
wherein g-C 3 N 4 The preparation method of (2) is as follows:
firstly, urea is placed in a crucible, the temperature is raised to 550 ℃ at the speed of 2 ℃/min, the urea is calcined in a muffle furnace for 2 hours, and the urea is naturally cooled to room temperature to obtain yellow solid,
then, the yellow solid is heated to 600 ℃ again at the speed of 2 ℃/min, calcined in a muffle furnace for 3 hours, naturally cooled to room temperature, and the obtained pale yellow solid is graphite-like phase carbon nitride g-C 3 N 4 。
(7) Will g-C 3 N 4 Adding the mixed solution into the fourth solution to obtain a suspension, wherein Li + Mass and g-C of doped rare earth up-conversion nanoparticles 3 N 4 The mass ratio is as follows: 3g Li + Doped rare earth up-conversion nano particles are correspondingly matched with 400mg g-C 3 N 4 . Adding the suspension into a high-pressure reaction kettle, maintaining at 200 ℃ for 20 hours, centrifugally collecting the product, and drying at 80 ℃ in vacuum for 16 hours to obtain Li + Doped rare earth up-conversion nano-particles/graphite-like phase carbon nitride composite materials.
Example 5: preparation of rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material
A preparation method of a rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material comprises the following steps:
(1) Nitrate Yb (NO) of lanthanoid 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 O is added into ethanol, and is stirred uniformly to prepare a first solution, the mol ratio of Yb to Ho in the first solution in the step (1) is 50:1,
(2) Dissolving sodium fluoride and lithium nitrate in the same organic volatile solvent as in the step (1), uniformly stirring to prepare a second solution,
(3) Slowly adding the second solution into the first solution, adding acid to adjust the pH value to 5, preparing a third solution,
(4) Transferring the third solution into a high-pressure reaction kettle, heating in a hydrothermal box at 200 ℃ for 20h, then naturally cooling,
(5) Centrifuging and washing the third solution after the hydrothermal treatment until the pH value is 6.5, and annealing the obtained precipitate for 2.5h at 525 ℃ to obtain Li + The particle size of the doped rare earth up-conversion particle material is 70 nm-80 nm,
(6) Li is mixed with + Dispersing the doped rare earth up-conversion nano-particle material in the same organic volatile solvent as in the step (1) to obtain a fourth solution, and carrying out g-C 3 N 4 Adding into deionized water, stirring to obtain g-C 3 N 4 The mixed liquid is prepared into a mixed liquid,
wherein g-C 3 N 4 The preparation method of (2) is as follows:
firstly, urea is placed in a crucible, the temperature is raised to 575 ℃ at the speed of 2.5 ℃/min, the urea is calcined in a muffle furnace for 2.5 hours, and the urea is naturally cooled to room temperature to obtain yellow solid,
then, the yellow solid is heated to 550 ℃ again at the speed of 2.5 ℃/min, calcined in a muffle furnace for 2.5 hours and naturally cooled to room temperature, and the obtained pale yellow solid is graphite-like carbon nitride g-C 3 N 4 。
(7) Will g-C 3 N 4 Adding the mixed solution into the fourth solution to obtain a suspension, wherein Li + Mass and g-C of doped rare earth up-conversion nanoparticles 3 N 4 The mass ratio is as follows: 2.5g Li + The doped rare earth up-conversion nano particles are correspondingly matched with 200mg g-C 3 N 4 . Adding the suspension into a high-pressure reaction kettle, maintaining at 190 ℃ for 22 hours, centrifugally collecting the product, and drying at 85 ℃ in vacuum for 14 hours to obtain Li + Doped rare earth up-conversion nano-particles/graphite-like phase carbon nitride composite materials.
Example 6: a method of making a solar cell comprising the steps of:
(1) Cleaning the FTO conductive glass substrate to obtain a clean and dry FTO conductive glass substrate,
(2) Dissolving stannous chloride dihydrate and urea in deionized water, oxidizing into tin oxide solution in air to obtain precursor solution of an electron transport layer, spin-coating the precursor solution of the electron transport layer on the FTO conductive glass substrate obtained in the step (1), annealing for 30min at 150 ℃ to obtain the electron transport layer,
(3) Li is mixed with + Spin-coating the precursor solution of the doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material on the electron transmission layer in the step (2), annealing for 10min at 90 ℃ to obtain an up-conversion nano-composite material layer,
the Li is + The precursor solution of the doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material is obtained by dispersing the nano-composite material in ethanol solvent,
(4) Will CH 3 NH 3 PbI 3 The mixed solvent of the solution, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is prepared according to the volume ratio of 9:1 preparing a perovskite precursor solution, spin-coating the perovskite precursor solution on an up-conversion nano composite material layer, dropwise adding chlorobenzene before spin-coating is finished, heating for 5min at 110 ℃ to obtain a perovskite absorption layer,
(5) And preparing an electrode on the perovskite absorption layer by adopting a screen printing method.
Example 7:
this embodiment differs from embodiment 6 in that:
in the step (2), annealing treatment is carried out for 10min at 180 ℃ to obtain an electron transport layer,
in the step (3), annealing is carried out for 30min at the temperature of 80 ℃ to obtain an up-conversion nano composite material layer,
in the step (4), finally heating for 10min at the temperature of 100 ℃ to obtain the perovskite absorption layer.
The remainder was the same as in example 6.
Example 8:
this embodiment differs from embodiment 6 in that:
in the step (2), annealing treatment is carried out for 15min at 170 ℃ to obtain an electron transport layer,
in the step (3), annealing is carried out for 15min at 70 ℃ to obtain the up-conversion nano composite material layer,
in the step (4), finally heating for 15min at 90 ℃ to obtain the perovskite absorption layer.
The remainder was the same as in example 6.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A rare earth up-conversion nano particle/graphite-like phase carbon nitride composite material is characterized in that the composite material is Li + Doped NaYbF 4 :Ho 3+ Rare earth up-conversion nanoparticles and g-C 3 N 4 Is obtained through the combination after the reaction,
NaYbF 4 :Ho 3+ rare earth up-conversion nano-particle is made of Yb 3+ And Ho 3+ Double doped up-conversion luminescent material of composition using Yb 3+ Is in the near infrared region and is effective in energy transfer from Yb 3+ Transfer to activator Ho 3+ Thereby converting near infrared light into visible light within the absorption range of the perovskite layer,
by preparing Li + Rare earth doped up-conversion nano particle material to change the frequency of incident sunlight, convert near infrared light into visible light which can be absorbed by the battery, thereby generating extra photocurrent, improving the battery efficiency,
graphite-like phase carbon nitride g-C 3 N 4 The perovskite material has an easily-adjustable energy band structure and a highly transparent morphology, is excellent in electron mobility and higher in conductivity, and is used for making up the defect of poor conductivity of the up-conversion nanoparticle material, and the functional groups on the perovskite material are used for further passivating perovskite defects.
2. A method of preparing the rare earth up-conversion nanoparticle/graphite-like phase carbon nitride composite material of claim 1, comprising the steps of:
(1) Nitrate Yb (NO) of lanthanoid 3 ) 3 ·5H 2 O and Ho (NO) 3 ) 3 ·5H 2 O is added into an organic volatile solvent and stirred uniformly to prepare a first solution,
(2) Dissolving sodium fluoride and lithium nitrate in the same organic volatile solvent as in the step (1), uniformly stirring to prepare a second solution,
(3) Slowly adding the second solution into the first solution, adding acid to adjust the pH value to 4-6, preparing a third solution,
(4) Transferring the third solution to an autoclave at 180 o C～220 o Heating in a hydrothermal box at the temperature of C for 4 h-24 h, naturally cooling,
(5) Centrifuging and washing the third solution after the hydrothermal treatment until the pH value is 6-7, and adding the obtained precipitate into a solution of 500 o C～550 o Annealing 2 h-3 h under C to obtain Li + The particle size of the doped rare earth up-conversion particle material is 50 nm-100 nm,
(6) Li is mixed with + The doped rare earth up-conversion nano-particle material is dispersed in the same organic volatile solvent as in the step (1) to obtain a fourth solution,
will g-C 3 N 4 Adding into deionized water, stirring to obtain g-C 3 N 4 The mixed liquid is prepared into a mixed liquid,
wherein g-C 3 N 4 The preparation method of (2) is as follows:
firstly, placing urea in a crucible, and adding urea in an amount of 2-3 o The C/min rate is raised to 550 o C～600 o Calcining 2 h-3 h in a muffle furnace, naturally cooling to room temperature to obtain yellow solid,
next, the yellow solid in the step (1) is pressed again by 2 to 3 o Heating to 500 deg.C/min o C～600 o Calcining 2-3 h in a muffle furnace, naturally cooling to room temperature, and obtaining pale yellow solid which is graphite-like phase carbon nitride g-C 3 N 4，
(7) Will g-C 3 N 4 Adding the mixed solution into the fourth solutionIn the process, a suspension is obtained, the suspension is added into a high-pressure reaction kettle, and the suspension is added into the high-pressure reaction kettle at 180 DEG o C～200 o C is kept for 20 to h to 24 hours, and the product is collected by centrifugation and is treated at 80 o C～90 o C vacuum drying 12 h-16 h to obtain Li + Doped rare earth up-conversion nano-particles/graphite-like phase carbon nitride composite materials.
3. The method of claim 2, wherein the molar ratio of Yb to Ho in the first solution in step (1) is from (40 to 60): 1.
4. A process according to claim 3, wherein the organic volatile solvent in step (1) is ethylene glycol.
5. The method of claim 4, wherein Li in the suspension of step (7) + Mass and g-C of doped rare earth up-conversion nanoparticles 3 N 4 The mass ratio is as follows: 2-3 g Li + The doped rare earth up-conversion nano particles are correspondingly matched with 100-400 mg g-C 3 N 4 。
6. The method according to claim 5, wherein the acid added in step (3) is HNO having a concentration of 65% 3 。
7. Perovskite solar cell prepared using the rare earth up-conversion nanoparticle/graphite-like phase carbon nitride composite material according to claim 1.
8. A method of preparing a perovskite solar cell as claimed in claim 7, comprising the steps of:
(1) Cleaning the FTO conductive glass substrate to obtain a clean and dry FTO conductive glass substrate,
(2) Dissolving stannous chloride dihydrate and urea in deionized water, oxidizing into tin oxide solution in air to obtain a precursor solution of the electron transport layer, and spin-coating the precursor solution of the electron transport layer in the step(1) The FTO conductive glass substrate obtained in the step (a) is at 150 o C～180 o Annealing for 10-30 min under the condition of C to obtain the electron transport layer,
(3) Li is mixed with + Spin-coating the precursor solution of the doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material on the electron transmission layer in the step (2), annealing for 10-30 min at 70-90 ℃ to obtain an up-conversion nano-composite material layer,
the Li is + The precursor solution of the doped rare earth up-conversion nano-particle/graphite-like phase carbon nitride composite material is obtained by dispersing the nano-composite material in ethanol solvent,
(4) Will CH 3 NH 3 PbI 3 The mixed solvent of the solution, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is prepared according to the volume ratio of 9:1 preparing a perovskite precursor solution, spin-coating the perovskite precursor solution on an up-conversion nano composite material layer, dropwise adding chlorobenzene before spin-coating is finished, heating for 5-15 min at 90-110 ℃ to obtain a perovskite absorption layer,
(5) And preparing an electrode on the perovskite absorption layer by adopting a screen printing method.
9. The method according to claim 8, characterized in that it comprises the steps of: in the step (3), annealing is carried out for 10 min-30 min at 80 ℃ to obtain an up-conversion nano composite material layer, and in the step (4), heating is carried out for 10min at 100 ℃ to obtain the perovskite absorption layer.
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